Aromatic aliphatic ether chlorides



vPatented July 15, 1941 .UNlTE-D 's ATEs PATENT OFFICE anom'ric aurna'rrc E'rnsn CHLORIDES AND rnocnss Herman A. Bruson, Philadelphia, Pa... assignor to- Riihm & Haas Company, Philadelphia, Pa.

No Drawing. Application March 29, 1938, Serial No. 198,697

Claims.

This invention relates to a process for preparing complex aryl polyalkylene. ether chlorides and aryloxy alkyl chlorides in which the aryl radical also carries another substituent. It relates further to a process whereby an aryl polyalkylene ether chloride or an aryloxy alkyl chloride is condensed with a compound having an alcoholic hydroxyl group, an olefine double bond or both in its. molecule, in the presence of a surface-active siliceous clay as a catalyst.

It also relates to certain new compounds which may be produced by this process.

It is known that'unsaturated compounds con taining olefinic linkages, or alcohols, can be condensed with the aryl polyalkylene halides by means of catalysts of the Friedel-Craft type as is described in the. co-pending. application of Bruson and Eastes, Serial N0.140,453, filed May 3, 1937. It is also known that 'compounds of similar type have been prepared by heating the substituted phenol with a dichloro ether in the presence of an alkali as shown by Bruson, U. S. Patents Nos. 2,097,441 and 2,098,203. Similar condensations between alcohols or oleflnes and aryloxy aliphatic compounds have also been brought about by means of anhydrous zinc which may contain other substituents which areinert in the process such as halogen atoms,

i two carbon atoms and n is an integer less than 8.

this type can be brought about in a simple and eflicient manner by heating the reactants in the presence' of certain clays which act as catalysts to cause the elimination of water in case one of the reactants is an alcohol or to cause the aryloxy alkylene chloride to combine with an unsaturated compound containing an olefine linkage. This reaction was entirelyunexpected since siliceous clays at high temperatures ordinarily decompose or rearrange ethers and one would, thereiore, expect complete break-down of aryloxy alkylene halides.

The clays which are most effective for the purpose of the present invention are primarily aluminum hydrosilicates which may contain combined magnesium, calcium, iron, titanium or other oxides. Many of these have a high absorptive capacity for the coloring matter in mineral oils and are known, therefore, as bleaching clays. Fullers earth and bentonite belong to this class and are suitable for the purposes of the present invention. Before usethey are preferably washed with acid and dried. at a temperature not'over C. In addition to these, there aremany clays marketed under registered, trademarks which are. also very suitable- These may be purchased on the open market under the names Tonsil," Atapulgas, Floridim Terrana" or Frankonite. These. clays are oi particular value as catalysts for the herein described reactions when one of the ingredients is a sensitive olefine or alcohol which is often decomposed or polymerized by Friedel-Craft typecatalysts.

Thearyl polyalkylene ether chlorides and the aryloxy alkyl chlorides which may be used in the process have the general formula R'--(o A),.c1

in which R.- is an arylrnucleus' such. as benzene, naphthalene, phenanthrene,-anthracene etc. and

hydroxy, alkoxy, aryloxy, hydrocarbon or acyl groups provided, of course, that the nucleus has at least one hydrogen atom available for reaction with the hydroxyl or olefinic compound, A represents an alkylene grou containing at least two carbon atoms which may be a straight or branched chain, or a polyalkylene ether radical in which the alkylene groups contain at least Typical ethers which may of the iollowing formulas:

and higher homologues. B. may be anyaryl be used are those group such as phenyl, 'naphthyl, phenahthryl,

ant-hracyl, etc.'and these groups may have other substituents as pointed out above.

These complex ether chlorides will condense with compounds having an alcoholic hydroigy group or an olefinic double bond-when a mint of such substances is heated to gtemperatur es above 150'C.,"preferably 180 to 210 C., in the presence of a surface-active siliceous clay, the radical of the olefine or alcohol uniting with the aryl nucleus of the complex ether chloride.

The reaction is applicable to compounds having an alcoholic hydroxyl group or an olefine double bond and which in addition may have other characteristic groups such as carboxylic, aromatic, arylaliphatic or cycloaliphatic groups.

The compounds containing olefinic double bonds which condense readily with the complex aryl ether chlorides may be hydrocarbons, unsaturated acids or their esters, unsaturated acids containing a hydroxyl group or an aromatic nucleus or a hydroaromatic substituent and the esters of such acids. Saturated acids containing a hydroxyl group or the esters of such acids may .logues.

Alcohols: aliphatic, arylaliphatic or hydroarylconditions of operation shown it may be otheraliphatic branched or straight chain, primary,

secondary or tertiary alcohols such as amyl, hexyl, o"c'tyl, decyl,1undecyl, dodecyl, myristyl, cetyl, oleyl, octadecyl, ceryl, myricyl and mixed aliphatic alcohols obtained from the hydrogenation of fats, or of carbon monoxide, octanol-2, montanic alcohol, benzyl alcohol, phenylethyl alcohol, methyl phenyl carbinol, decahydronaphthol, cholesterol, etc.

Hydroxy acids: 10-hydroxy stearic, ricinoleic.

9,10-dihydroxy stearic, ll-hydroxy undecylic, phenyl hydroxy stearic, cyclohexylhydroxy stearic and the esters of these acids.

The condensation is carried out in general by heating a mixture of the complex ether chloride under a reflux condenser equipped with a water trap. The elimination of water may be brought about by carrying out the reaction in the presence of a solvent which does not take part in the reaction and which boils between about 150 and 250 C. The saturated cycloaliphatic hydrocarbons, such as decaline, and saturated petroleum hydrocarbons having the proper boiling range are suitable for the purpose. The amount of clay us'ed is usually 10% to 20% by weight calculated on the combined weight of the reactants. More or less may be used but the above amount gives satisfactory results. After thecondensation is complete, the clay is filtered off and the product purified by fractional distillation, preferably under reduced pressure.

The following examples will serve to illustrate the invention which, however, is not limited to the exact reactants, clays, temperature and other wise practiced within the scope of the appended claims.

Exmu: 1 p-Iso-undecylphenoru-p'-chl0rodiethyl ether A mixture consisting of 103 g. of 5-ethyl-nonanal-2 120 g. of fl-phenoxy-p-chlorodiethyl ether and 15 g. of Tonsil AS" (registered trade-mark) 185 C. for five hours with continuous agitation.

The reaction product was filtered while hot, by means of suction, and the clear, almost colorless filtrate iractionally distilled under reduced pressure. The product, boiling above 155 C./0.5-1 mm., was rei'ractionated and yielded 61 g, of an iso-undecylphenoxyethoxy ethyl chloride boiling at 190 to 195 0. at about 1 mm., containing 9.7% chlorine (theory 10.0% chlorine) and 40 g. of an isomeric iso-undecylphenoxyethoxy ethyl chloride boiling at 200-220 C./1 mm.

Other aliphatic alcohols, such as dodecyl, te-

ztradecyl, cetyl, oleyl, or octadecyl alcohol, can be used mol tor mol in place of the 5-ethyl-nonanol-2 to yield the corresponding alkyl phenoxyethoxyethyl chlorides.

Exnirm: 2

5- (Sec. octyl-z naphthory) -p'-chlorodiethyl ether A mixture consistingof g. of octanol-2, 75 g.

' The filtered reaction product, after fractionation in vacuo, yielded the compound as a pale yellow oil boiling at 210-220 C./1 mm.

The octanol-2' can be replaced by hexanol-2, heptanol-2, or nonanol-2 to yield the homologous sec. hexyl-, sec, heptyl-, and sec. nonyl-naphthoxyethoxy ethyl chlorides, which are highboiling yellow oils.

The above mixture was heated, while stirring for one-half hour, to 180 C., under a reflux condenser attached to a water trap, during which time 6 cc. of water collected in the trap. The

temperaturewas then maintained at 180 C. for four hours, during which time 2 co. more water came over. The product was filtered hot and the excess fl-phenoxy-p'-chlorodiethyl ether recovered by iractionati'on in vacuo. In this manner, 135 g. of fi-phenoxy-p'-chlorodiethyl ether boiling at 113-120 C./1 mm. was recovered. The residual oil was heated under 1' mm. pressure to 220 C.. but no unchanged ethyl recinoleate distilled over. The dark residual oil,

weighing 145 g., was bleached by heating at 100 C. for minuteswith 10 g. of Tonsil clay and filtered hot. It formed a yellow 011. Analysis showed 7.31% chlorine. and an acid number 23,

EXAMPLE 4 A mixture consisting of 91 g. of oleic acid,

A mixture consisting of 180 g. of p-phenoxy-p'- chlorodiethy'l' ether, 117 g. of octanol-2, and g. 01' Tonsil clay was heated with stirring for four hours at 160-175 C. under reflux attached .to

a watertrap. The sec. octyl-phenoxy-ethoxyethyl chloride was obtained in 60% yield as a pale yellow oil, B. P. 175-185 C./3 mm.

Exauru: 9

. A mixture, consisting of 109 g. of ethyl-10 hydroxy stearate, 122 g. of fl-phenoxy-p-chlorodiethyl ether and 23 g. of Tonsil clay, was stirred and heated for four hours at 180to 185 C. under a reflux condenser attached to a water trap. The product was filtered and the filtrate distilled in vacuo at 1-2 mm. until the vapor temperature reached'210 C. The still residue, weighing 127 134 g. of p-phenoxy-fi'-chlorodiethyl ether, and

23 g. of Tonsil clay was heated with stirring for four hours at 185 to 200 C. under a reflux condenser. The filtered product was then distilled in high vacuo to remove all unchanged materials until the vapor temperature reached 200 C./0.5 mm. The residue was a reddish oil weighing 110 g. and contained 6.5% chlorine.

The resulting chloroethoxyethoxy phenyl stearic acid may be converted to esters or salts of organic or inorganic bases as desired.

EXAMPLE 5 A mixture consisting of 61 g. of methylphenyl carbinol, 150 g. of p-phenoxy-p'-chlorodiethyl ether, and 20 g. of Tonsil clay was stirred and heated for four hoursfat 180 to 190 C. under reflux attached to a water trap. The filtered product was fractionally distilled in vacuo. The compound cH-c.H.-0-cmem-o-cmomci CH:

distilled over at 190-205 C./2 mm. as a pale yellow oil with a blue fluorescence.

Examrrs 6 A mixture onsistingof 100 g. of p-phenoxy-p'- chlorodiethyl ether, 54 g. of benzyl alcohol and 7.7 g. of Tonsil clay was stirred and heated for three hours at 170 to 180 C. under reflux attached to a water trap. The product was filtered and the filtratefractionated in vacuo.

Benzylplienoxyethoxyethyl chloride came over at 200-220 C. /3 mm.

EXANiPLE 7 A mixture, consisting of 80 g. of p-phenoxy-p chlorodiethyl ether, 10 g. of Tonsil clay, and 49 g. of higher alcohols from the methanol synthesis, boiling at 190 to 210 C. and consisting of mixed primary and secondary branched chain 'monohydric alcohols, containing from about 9 to 12 carbon atoms resulting from the catalytic reduction of carbon monoxide with hydrogen, was heatedfor four hours, with stirring under reflux g., was clarified with bleaching clay. It contained 6% chlorine by analysis. Theoretical chlorine- This ester may be saponii-led with alkali and thefree acid obtained by acidityingthe solution of the alkali metal salt. From this acid other esters and salts of organic or inorganic bases can be prepared in any conventional manner.

ExAmLn 10 A mixture consisting of 95 g. of methyl undecylenate, 150 g. of p-phenoxy-p'-chlorodiethyl ether and 25 g. of Tonsil clay was stirred and heated under reflux attached to a water trap, for flvehours at 170 to 190 C. The filtered product was distilled under reduced pressure. There was obtained 60 g. of pale yellow oil boiling at 200 220 C./1mm., containing 9.38% .of chlorine and I having the probable formula I 01cmcm-o-cn,cm-o-o.m--on(cmlto00cm This ester may be saponified with alkali and the free acid obtained by acidifying the solution oi-the alkali metal salt. From this acid other attached to a water trap. The filtered product,

upon fractionation in vacuo, yielded the mixed C9-C1: alkylphenoiwethoxyethyl chlorides as a pale yellow oil boiling at 180-220 C./2 mm..

esters and salts'of organic or inorganic bases can be prepared in any conventional manner.

Exmrrr: 11

A mixture, consisting of 56 g. of p-phenoxyethyl I chloride, 66.5 g. of dodecyl alcohol, and 15 g. of

acid-washed Tonsil bleaching earth, was refluxed three and one-quarter hours at 167 to 195 'C., during which time 2.5 cc. 01' water was removed in a. separator and the remaining distillate returned to the reaction mixture. Heating was continued for an additional sixteen hours at 195 to 181 C. The reaction mixture was diluted with toluene, filtered from the clay, and distilled in vacuo. The p-chloro ethyl ether of dodecyl phenol was obtained as a pale yellow oil, 97.5%

pure, B. P. 180-200 C./1 mm. I

Err/turns 12 A mixture consisting of 112 g. of n-butyl-oleate (B. P. 178-188 C./1 mm.), g. of fi-phenoxyp'-chlor0diethyl ether and 20 g. of Tonsil clay was heated under reflux, with rapid stirring, for

about six hours at 186 to 195 C.. The filtered oil was then distilled in vacuo until the vapor temperature reached 210 C. at 1 mm. pressure. The residue, weighing g., was a dark oil containing 5.5% chlorine andhaving an acid number 88.4, indicating substantial addition of the phenyl nucleus to the double bond had occurred, together with some hydrolysis of the ester group.

This ester may be saponified with alkali and the free acid obtained by acidifying the solution of the alkali metal salt. From this acid other esters and salts of organic or inorganic bases can be prepared in any conventional manner.

EXAMPLE 13 A mixture, consisting of 76 g. of decahydro-pnaphthol, 100 g. of c-phenoxy-p'-chlorodiethyl ether, and 18 g. of Tonsil clay, was stirred and heated under reflux attached to a water trap, for four and one-half hours at 180 to 200 C. The filtered product was distilled in vacuo to yield decahydronaphthylphenoxyethoxyethyl chloride as a greenish fluorescent oil boiling at 210-220 C./2 mm.

The compounds prepared according to Examples 3, 4, 9, l and 12 are all derivatives of substituted fatty acids in which the substitent is a chloralkoxy aryl group or a chloropolyalkoxy aryl group. The esters, the corresponding acids and salts may be expressed by the general formula Cl(OA)nR'Y-COOM in which A,

n and R have the meanings given above, Y is an' aliphatic hydrocarbon chain which may also have a double bond or an aromatic or hydroaromatic substituent, and M is hydrogen, a hydrocarbon radical or a basic organic or inorganic salt-forming group or a metal.

All of the complex aryloxy alkyl or aryl polyalkylene ether chlorides described herein are usefulintermediates for preparing water-soluble capillary-active compounds. For example, the aromatic ring may be sulfonated to yield watersoluble sulfonic acids which along with their water-soluble salts of organic or inorganic bases are good wetting, cleansing, dispersing and emulsifying agents. The terminal chlorine atom may be replaced by an S0sNa group as is described in my co-pending application Serial No. 187,158 filed January 27, 1938 by heating the complex ether chloride with aqueous sodium sulfite. The

free sulfonic acid can be prepared from the sodium salt and can be converted into other salts of organic or inorganic bases.

The complex aryl ether halides also react with ammonia, primary, secondary or tertiary amines which may contain sulfonic or carboxylic acid groups whereby the RR'--i0-A)1lgroup is attached to the nitrogen atom and forms amines or quaternary ammonium salts.

Thio ethers may be prepared by heating the complex ether with sodium sulfide and the mercaptans by heating with sodium hydrosulfide.

is a member of the group consisting of aliphatic, arylaliphatic and hydroarylaliphatic radicals, R

is an aryl nucleus, A is selected from the group general formula RR'(OA) C1 in which R is an aliphatic radical, R is an aryl nucleus, A isselected from the group consisting of alkylene radicals containing at least two carbon atoms and polyalkylene ether radicals containing at least two carbon atoms in each alkylene group and n is an integer less than 8, which comprises heating in the presence of a surface-active siliceous clay an ether chloride R'(OA) Cl and an aliphatic alcohol.

3. The process of preparing compounds of the general formula RR'(O-A)1.Cl in which R is an aliphatic radical, R is an aryl nucleus, A is selected from the group consisting of alkylene radicals containing at least two carbon atoms and polyalkylene ether radicals containing at least two carbon atoms in each alkylene group and n is an integer less than 8, which comprises heating in the presence of a surface-active siliceous clay an ether chloride R'(OA)nC1 and an oleflne.

4. The process of preparing compounds of the general formula RCsH4(O-A) "Cl in which R is an aliphatic radical, A is a member of the group consisting of alkylene radicals containing at least twocarbon atoms and polyalkylene ether radicals containing at least two carbon atoms in each alkylene group and n is an integer less than 8, which comprises heating in the presence of a surface-active clay an ether chloride CsH5(OA)1|C1 and an aliphatic alcohol.

5. The process of preparing compounds of the general formula RC6H4(o-A) "C1 in which R is an aliphatic radical, A is a member of the group consisting of alkylenev radicals containing at least two carbon atoms and polyalkylene ether radicals containing at least two carbon atoms in each alkylene group and n is an integer less than 8, which comprises heating in the presence of a surface-active clay an ether chloride CaHe-(0,A)Cl

CeHsOCI-hCI-IzOCHzCHzCl and a member of the group consisting of ali- In the foregoing description the complex ether chlorides have been used as illustrations. It is, of course, possible to carry out the same reactions' with the corresponding bromides and iodides.

I claim:

1. The process of preparing compounds of the general formula R-R'(OA)Cl in which R phatic, arylaiiphatic, and hydroaryialiphatic alcohols and olefinic hydrocarbons.

. '7. The process of preparing a compound of the formula RCeH4OCH2CH2OCH2CI-I2Cl in which R is 'an aliphatic group which comprises heating in the presence of a surface-active clay the compound CsHsOCHzCHaOCHzCHzCl'flnd an aliphatic alcohol.

8. The process of preparing a compound of the formula RC6H4OCH2CH2OCH2CH2C1 in which R is an aliphatic group which comprises heating in the presenceot a surface-active clay the compound CsHsOCHzCHzOCHzCHzCI and an 01811116.

9. The process of preparing C12H25.CBH4OCH2CH2OCH2CH2CI which comprises heating in the presence of a 10. The process or preparing RCoH4OCH2CH2OCHaCH2C1 wherein R represents a branched chain aliphatic 5 hydrocarbon group of approximately 9 to 12 carbon atoms which comprises heating in the presence 01' a surface-active clay between about 150 C. and about 210' C. a mixture of p-chloroethoxyethoxy benzene and higher alcohols obtainable surface-active clay between about 150 C. and from the methanol synthesis andboiling a about 210 C. CsHsOCI-IzCI-IzOCI-IaCHzCl and dodecyl alcohol.

190 C. to 210 C.

HERMAN A. BRUSON. 

